EP4043526A1 - Thermoplastic composition of polycarbonate and polyester - Google Patents

Thermoplastic composition of polycarbonate and polyester Download PDF

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Publication number
EP4043526A1
EP4043526A1 EP21156855.5A EP21156855A EP4043526A1 EP 4043526 A1 EP4043526 A1 EP 4043526A1 EP 21156855 A EP21156855 A EP 21156855A EP 4043526 A1 EP4043526 A1 EP 4043526A1
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EP
European Patent Office
Prior art keywords
composition
ethylene
acid
polycarbonate
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP21156855.5A
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German (de)
French (fr)
Inventor
Anirban GANGULY
Roshan Kumar Jha
Susanta MITRA
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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Priority to EP21156855.5A priority Critical patent/EP4043526A1/en
Priority to KR1020237030907A priority patent/KR20230150307A/en
Priority to CN202280021350.9A priority patent/CN117043271A/en
Priority to US18/276,964 priority patent/US20240150571A1/en
Priority to PCT/EP2022/051019 priority patent/WO2022171401A1/en
Priority to EP22701568.2A priority patent/EP4291610A1/en
Publication of EP4043526A1 publication Critical patent/EP4043526A1/en
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869Acids or derivatives thereof
    • C08L23/0876Neutralised polymers, i.e. ionomers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/30Applications used for thermoforming
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/53Core-shell polymer

Definitions

  • the present invention relates to a thermoplastic composition comprising polycarbonate and polyester.
  • the present invention further relates to an article comprising or consisting of such a composition.
  • compositions comprising polycarbonate and polyester have excellent appearance, mechanical properties, dimensional stability, and chemical resistance, and are widely used in various fields.
  • a composition composed of polycarbonate (PC) and poly(butylene terephthalate) (PBT) has characteristics of imparting excellent impact resistance (including low temperature impact resistance or ductility), mechanical property, and dimensional stability to the polycarbonate.
  • PC polycarbonate
  • PBT poly(butylene terephthalate)
  • JP2008115295A discloses a highly-processable polymer material composed of a polycarbonate / polyester resin with a compatilizer which is an olefin copolymer having a functional group which reacts with a carboxyl group which has outstanding impact resistance and can improve quality stability.
  • CN105385117A discloses high-/low-temperature-impact-resistance PC-PBT composite material for LED (Light Emitting Diode) aluminum-plastic structural parts.
  • CN108034204B discloses low-temperature impact resistant polyester compositions, wherein the composition is prepared from PBT resin with MBS toughening agent, compatilizer, ester exchange inhibitor, antioxidant and lubricant, and the preparation method of the low-temperature impact resistant polyester composition is also disclosed.
  • CN105255149A discloses low-temperature toughened and reinforced PC/PBT alloy materials and a preparation method thereof, wherein low-temperature impact property of the alloy is improved by adding a low-temperature toughening agent.
  • PC/PBT polybutylene terephthalate
  • compositions comprising polycarbonate and poly(ethylene terephthalate) (PC/PET) have been reported to have better thermal properties and more surface gloss compared to PC/PBT compositions.
  • PET is a widely available, well-known material, used for a variety of applications including in particular bottles, such as for carbonated and non-carbonated soft drinks, fibers, and packaging, household and consumer products.
  • PC/PET compositions are found to show less favorable low temperature ductility, i.e. ductility at temperatures in the range of about - 20 to about -30 °C.
  • silicone-modified polycarbonate copolymer may be used, which, however is not cost effective.
  • an object of the invention to provide for a composition comprising PC and PET that has improved low temperature impact resistance properties without significantly affecting or even improving the mechanical and other properties such as thermal properties.
  • compositions comprising polycarbonate and polyester, wherein said polyester comprises poly(ethylene terephthalate), an impact modifier in combination with a specific ionomer demonstrates an improved low temperature impact resistance (without affecting mechanical and other thermal properties) compared to an otherwise identical composition wherein the poly(ethylene terephthalate) component does not contain the ionomer.
  • the present inventors believe that the presence of the specific monovalent ionomer acts as an impact synergist and helps by acting as intrinsically self-healable materials, which generates instantaneous impulsive fracture/ crack or propagation resistance without any external trigger. This makes it suitable for impact resistant application where better ductility is desired.
  • thermoplastic composition comprising, based on the weight of the composition, at least 30 wt. % aromatic polycarbonate, at most 70 wt. % of polyester comprising poly(ethylene terephthalate), from 0.1 - 20 wt. % of an impact modifier, from 0.05 to 1.0 wt. % of a monovalent ionomer comprising repeat units derived from ethylene, a dicarboxylic acid or derivative thereof, a monocarboxylic acid, and optionally a comonomer.
  • composition according to the invention as presented herein is a thermoplastic composition.
  • Polycarbonate is a well-known material and generally exhibits good mechanical and optical properties. Typical applications include optical media carriers, glazing, extruded sheets, lenses and water bottles. Polycarbonates are generally manufactured using two different technologies. In a first technology, known as the interfacial technology or interfacial process, phosgene is reacted with bisphenol A (BPA) in a liquid phase. Another well-known technology for the manufacture of polycarbonate is the so-called melt technology, sometimes also referred to as melt transesterification or melt polycondensation technology. In the melt technology, or melt process, a bisphenol, typically BPA, is reacted with a carbonate, typically diphenyl carbonate (DPC), in the melt phase.
  • BPA bisphenol A
  • DPC diphenyl carbonate
  • melt polycarbonate obtained by the melt transesterification process is known to be structurally different from polycarbonate obtained by the interfacial process.
  • melt polycarbonate typically has a minimum amount of Fries branching, which is generally absent in "interfacial polycarbonate”.
  • melt polycarbonate typically has a higher number of phenolic hydroxy end groups while polycarbonate obtained by the interfacial process is typically end-capped and has at most 150 ppm, preferably at most 50 ppm, more preferably at most 10 ppm of phenol hydroxyl end-groups.
  • the polycarbonate comprises or consists of aromatic bisphenol A polycarbonate homopolymer (also referred to herein as bisphenol A polycarbonate) and not copolymers of polycarbonates.
  • the polycarbonate of the invention disclosed herein comprises at least 30 wt. %, preferably at least 60 wt. % of bisphenol A polycarbonate based on the total amount of polycarbonate. More preferably, the polycarbonate in the composition essentially consists or consists of bisphenol A polycarbonate.
  • the polycarbonate has a weight average molecular weight of 15,000 to 60,000 g/mol determined using gel permeation chromatography with polycarbonate standards.
  • the polycarbonate is an interfacial polycarbonate.
  • the polycarbonate is a melt polycarbonate.
  • the polycarbonate is a mixture of from 20 - 80 wt. % of interfacial polycarbonate and from 80 - 20 wt. % of melt polycarbonate, based on the weight of the polycarbonate.
  • the polycarbonate may be a mixture of two or more polycarbonates differing in melt volume rate (i.e. in molecular weight).
  • the polycarbonates of the mixture may both be a bisphenol A polycarbonate homopolymer.
  • the polyester of the composition disclosed herein comprises, essentially consists of or consists of PET.
  • the PET may be a mixture of two or more different poly(ethylene terephthalate)s, for example a mixture of PETs with mutually different intrinsic viscosities.
  • the polyester may further comprise recycled poly(ethylene terephthalate).
  • Polyesters like poly(ethylene terephthalate) are known to a skilled person per se.
  • the polyester can be prepared by direct polyesterification of terephthalic acid with 1,2-ethane diol (ethylene glycol), usually with the help of a strong acid catalyst in the presence or absence of co monomers like isophthalic acid (IPA).
  • IPA isophthalic acid
  • the composition comprises at most 40 wt. % of polyester comprising poly(ethylene terephthalate) based on the weight of the composition and wherein the combined weight percent value of all components is 100 wt.%. It is preferred that the PET has an intrinsic viscosity of 0.4 to about 2.0 dl/g as measured in a 3:2 weight to weight mixture of phenol: 1,2-dichlorobenzene at 25°C.
  • the polyester may further comprise another polyester, miscible with poly(ethylene terephthalate), which is preferably poly(butylene terephthalate) (PBT).
  • the composition preferably comprises from 99 to 80 wt. % of poly(ethylene terephthalate) and 1 to 20 wt. % of poly(butylene terephthalate) based on the weight of the polyester.
  • the thermoplastic composition of the invention comprises an impact modifier.
  • Suitable impact modifiers are typically high molecular weight elastomeric materials derived from olefins, monovinyl aromatic monomers, acrylic and methacrylic acids and their ester derivatives, as well as conjugated dienes.
  • the polymers formed from conjugated dienes can be fully or partially hydrogenated.
  • the elastomeric materials can be in the form of homopolymers or copolymers, including random, block, radial block, graft, and core-shell copolymers. Combinations of impact modifiers can be used.
  • the impact modifier is preferably selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene-methyl-acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, low density polyethylene, maleic anhydride grafted ethylene-octene copolymer, ethylene-ethyl acrylate-glycidyl ester copolymer, ethylene-butyl acrylate-glycidyl ester copolymer, rubber modified styrene-acrylonitrile copolymer, rubber modified styrene-acrylonitrile-methyl methacrylate copolymer, styrene-acrylonitrile copolymer and combinations of at least two of the foregoing (co)polymers.
  • the amount of impact modifier may be from 0.1 - 20 wt.% based on the weight of the composition.
  • the impact modifier is comprised in the composition in an amount of from 2 - 15 wt.%, preferably from 8 - 12 wt.%.
  • composition of the invention comprises an impact synergist, which is a monovalent ionomer comprising repeat units derived from ethylene, a dicarboxylic acid or derivative thereof, a monocarboxylic acid, and optionally a comonomer.
  • Ionomers are synthetic polyelectrolytes that consist of both electrically neutral and ionized groups that are randomly and/or regularly distributed along the polymer backbone.
  • One important characteristic of ionomers is the strong molecular aggregation of the ion-carrying groups to ion rich domains or ion clusters, which act as physical crosslinks. When heated, the ionic bonds and clusters dissolve and when cooled, they reform. This gives ionomers a unique structure and behavior. At low temperatures, they behave like crosslinked polymers (elastomers) and at elevated temperatures like ordinary thermoplastics. The majority of ionomers studied have a polyvinyl or polydiene backbone and carry anionic groups (anionomers) with Na + , and Zn 2+ as counter ions.
  • ionic copolymers have typically a low melting point, improved toughness/flexibility and mechanical strength and when used as films, possess a much higher clarity and gloss and provide superior hot tack, seal strength and puncture resistance than unmodified polyethylene film.
  • EAA ethylene acrylic acid copolymer
  • Surlyn ethylene acrylic acid copolymer
  • Other important applications include coatings and surface films for golf balls, sports equipment, and for over molded (cosmetic) bottles.
  • the composition comprises from 0.05 to 1.0 wt. %, preferably from 0.1 to 0.5 wt. % of a monovalent ionomer comprising repeat units derived from ethylene, a dicarboxylic acid or derivative thereof, a monocarboxylic acid, and optionally a comonomer; based on the weight of the composition.
  • the monocarboxylic acid is selected preferably from (meth)acrylic acid.
  • the dicarboxylic acid is preferably selected from maleic acid, fumaric acid, itaconic acid, maleic anhydride, fumaric anhydride, itaconic anhydride, one or more C1-4 alkyl half ester of maleic acid, one or more Ci-4 alkyl half ester of fumaric acid, one or more C1-4 alkyl half ester of itaconic acid, or combinations of two or more thereof.
  • the comonomers is preferably selected from CO, acid anhydride, maleic acid, monoester of the acid anhydride, an epoxy-containing (meth)acrylate, or combinations of two or more thereof.
  • the carboxylic acid functionalities in the aforesaid ionomer are at least partially neutralized (from about 10 to about 70 %, about 35 to about 70 %) by a monovalent ion, preferably selected from alkali metal ions, more preferably from sodium or potassium.
  • a monovalent ion preferably selected from alkali metal ions, more preferably from sodium or potassium.
  • Typical additives that are used in the composition can comprise one or more of a flow modifier, filler, reinforcing agent (e.g., glass fibers or glass flakes), antioxidant, heat stabilizer, light stabilizer, UV light stabilizer and/or UV absorbing additive, plasticizer, lubricant, release agent, in particular glycerol monostearate, pentaerythritol tetra stearate, glycerol tristearate, stearyl stearate, antistatic agent, antifog agent, antimicrobial agent, colorant (e.g., a dye or pigment), flame retardant either or not combined with an anti-drip agent such as polytetrafluoroethylene (PTFE) or PTFE-5 encapsulated styrene-acrylonitrile copolymer.
  • a flow modifier e.g., filler, reinforcing agent (e.g., glass fibers or glass flakes), antioxidant, heat stabilizer, light stabilizer, UV light stabilizer
  • composition disclosed herein may comprise one or more nucleating agents.
  • nucleating agent refers to an additive that enhances the formation of crystals in the polyester phase of the composition. Addition of a nucleating agent will accordingly increase the crystallinity of the polyester phase, which results in an increased heat resistance.
  • the composition may comprise from 0.01 to 5 wt.% by weight of nucleating agent(s).
  • compositions can be manufactured by various methods known in the art. For example, polycarbonate, polyester, and other components are first blended, optionally with any fillers or additives, in a high-speed mixer or by hand mixing. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components can be incorporated into the composition by feeding it directly into the extruder at the throat and/or downstream through a side feeder, or by being compounded into a masterbatch with a desired polymer and fed into the extruder. The extruder was set with barrel temperatures between 150°C and 260°C. The extrudate can be immediately cooled in a water bath and pelletized. The pellets so prepared can be one-fourth inch long or less as desired. Such pellets can be used for subsequent molding, shaping, or forming.
  • compositions can be molded into articles by a variety of methods, such as injection molding, extrusion, and thermoforming.
  • articles include automotive and vehicular body panels such as bumper covers and bumpers or a housing for electrical equipment.
  • the present invention relates to an article comprising or consisting of the composition disclosed herein. More in particular, the present invention relates to vehicular body parts or for housing of electrical equipment comprising or consisting the composition disclosed herein. Likewise, the present invention relates to a vehicle or an electrical equipment comprising said vehicular body part or said housing. The present invention relates to the use of the composition disclosed herein for the manufacture of an article of manufacture, such as an automotive part.
  • the composition comprises at least 30 wt. % aromatic polycarbonate and at most 70 wt. % of polyester comprising poly(ethylene terephthalate).
  • the amount of polycarbonate is preferably from 30 wt.% - 90 wt.% such as from 55 wt.% - 70 wt.% and the amount of polyester is preferably from 10 - 70 wt.% such as from 30 wt. % - 50 wt. %.
  • the monovalent ionomer is produced by neutralizing all or part of the carboxylic acid using a monovalent ion, preferably selected from alkali metal ions, more preferably from sodium or potassium.
  • the total weight of the composition will represent 100 wt.% and that any combination of materials which would not form 100 wt.% in total is unrealistic and not according to the invention.
  • the total of the components making up the thermoplastic composition disclosed herein is 100 wt.%.
  • VST Vicat softening temperature
  • HDT Heat distortion temperature
  • the molecular weight of the polycarbonate and poly(butylene terephthalate) was measured by GPC method with polystyrene standard in an Agilent 1260 Infinity (SYS-LC-1260) equipment with PLGel 5 ⁇ m Minimix C 250 x4.6 mm column and Refractive Index detector. The sample is dissolved in dichloromethane and the same solvent is used as carrier. Fries branching The amount of Fries branching was determined using an Agilent 1100series HPLC equipped with a MWD G1365B detector. The column is an Agilent Zorbax Eclipse XDB-C18 4.6 x 75 mm. The injection volume is 50ml.
  • the oven temperature is 35 °C and the wavelength to acquire data is 320.16 nm.
  • 0.3g of sample is dissolved in 7.5 ml of a solvents mixture based on 5 ml of tetrahydrofuran and 2.5 ml of a 10 % of potassium hydroxide solution in methanol, after heating this sample at 40°C during 20 min, 1.4 ml of acetic acid is added.
  • End Cap Level The endcap level was determined based on UV measurement to determine the amount of terminal OH groups. Combined with the number average molecular weight the endcap level is then determined in accordance with formula below.
  • % EC 100 ⁇ ppmOH ⁇ Mn 340000 wherein % EC is the endcap level, ppm OH is the amount of hydroxyl end groups in parts per million by weight and Mn is the number average molecular weight of the polycarbonate based on polycarbonate standards.
  • the UV spectrophotometer was a Perkin Elmer Lambda 800. Measurements were carried out on 0.01g of a polycarbonate sample diluted in 10 ml of dichloromethane and placed into a quartz cuvette of 10 mm of optical path. The wavelength to acquire data are 284 and 292 nm.
  • Glass transition temperature (T g ) Glass transition temperatures were determined by dual cantiliver three point bending dynamic mechanical analyzer wherein the temperature was increased from 23 °C to 250 °C and frequency of 6.28 rad/sec.
  • Melt volume rate (MVR) The melt volume rate was determined in accordance with ISO 1133-1:2011. For polycarbonate, measurements were carried out at a temperature of 300°C and a load of 1.2 kg. For the compositions, measurements were carried out at a temperature of 250°C and a load of 5.0 kg.
  • the examples were made by extruding on a WP 25 millimeter (mm) co-rotating intermeshing twin-screw extruder having L/D of 41.
  • the components of the compositions and their source are listed in Table 1. All components were dry-mixed and added to the throat of the extruder.
  • the extruder was set with barrel temperatures between 150°C and 260°C.
  • the material was run maintaining torque of 55-60% with a vacuum of 100 millibar (mbar) - 800 mbar applied to the melt during compounding.
  • the composition was pelletized after exiting the die head.
  • Table 1 Components of the compositions and their source PC1 Bisphenol A polycarbonate manufactured using an interfacial process, having a melt volume rate of 6 cc/10 min, and endcap level of about 100%, available from SABIC (PC 105) PET1 Polyethylene terephthalate having an intrinsic viscosity of 0.84 dl/g as measured in a 3:2 weight to weight mixture of phenol: 1,2-dichlorobenzene at 25°C containing 1.85wt.% Isophthalic acid comonomer available from SABIC ( BC 212) IM1 MBS core shell impact modifier commercially available from Dow, Singapore (Paraloid MBS EXL 2690) Stab Stabilizer - hindered phenol Antioxidant Irganox 1010 from BASF Quench Mono Zinc Phosphate quencher Iono1 Surlyn PC100 , Na + ionomer
  • Table 2 The amounts in Table 2 are in weight percent based on the total weight of the composition. In all the examples, the total amount of components, equals 100 weight percent. Table 2 shows that the composition comprising the Na+ ionomer impact synergist surprisingly shows improved low temperature (at -20°C and -30°C) impact resistance property, without compromising on the thermal properties as demonstrated by HDT, VST, Tg results. When comparing C1 with E1 & E2, it is observed there is an increase of at least two times in the low temperature impact resistance property resulting from the addition of the Na+ ionomer impact synergist. E3 & E4 shows similar experiments with lower and higher concentrations of the ionomers respectively.
  • E2 and E5 demonstrate the properties of the composition comprising the Na+ ionomer and the Zn ++ ionomer impact synergists respectively. Comparing CE1 & E2 to E3, it can be seen that presence of Zn ++ ionomer does not improve the low temperature impact properties as shown in Table 3.
  • Table 3 Formulations and properties for the PC - PET composition with Na + and Zn ++ ionomer impact synergist Components (wt.
  • E6 and E7 demonstrate the use of different types of known nucleating agents to improve heat properties of PC/PET composition as shown by higher VST and HDT compared to CE1. However, these nucleating agents in E6 and E7 do not show any improvement in low temperature impact properties.
  • nucleating agents are added into the PC/PET composition comprising the Na + ionomer impact synergist. No significant improvement in low temperature impact properties is observed, although improvement in heat properties are achieved.
  • Table 4 Formulations and properties for the PC - PET composition with Na + ionomer impact synergist in combination with nucleating agent Components (wt.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The present invention relates to a composition comprising at least 30 wt. % aromatic polycarbonate and at most 70 wt. % of polyester comprising poly(ethylene terephthalate), from 0.1 - 20 wt. % of an impact modifier, and from 0.05 to 1.0 wt. % of a monovalent ionomer comprising repeat units derived from ethylene, a dicarboxylic acid or derivative thereof, a monocarboxylic acid, and optionally a comonomer; based on the weight of the composition. The present invention further relates to an article comprising or consisting of such a composition.

Description

  • The present invention relates to a thermoplastic composition comprising polycarbonate and polyester. The present invention further relates to an article comprising or consisting of such a composition.
  • Compositions comprising polycarbonate and polyester have excellent appearance, mechanical properties, dimensional stability, and chemical resistance, and are widely used in various fields. Particularly, a composition composed of polycarbonate (PC) and poly(butylene terephthalate) (PBT) has characteristics of imparting excellent impact resistance (including low temperature impact resistance or ductility), mechanical property, and dimensional stability to the polycarbonate. These compositions are useful in fields such as interior and exterior parts in automobiles specifically.
  • JP2008115295A discloses a highly-processable polymer material composed of a polycarbonate / polyester resin with a compatilizer which is an olefin copolymer having a functional group which reacts with a carboxyl group which has outstanding impact resistance and can improve quality stability.
  • CN105385117A discloses high-/low-temperature-impact-resistance PC-PBT composite material for LED (Light Emitting Diode) aluminum-plastic structural parts.
  • CN108034204B discloses low-temperature impact resistant polyester compositions, wherein the composition is prepared from PBT resin with MBS toughening agent, compatilizer, ester exchange inhibitor, antioxidant and lubricant, and the preparation method of the low-temperature impact resistant polyester composition is also disclosed.
  • CN105255149A discloses low-temperature toughened and reinforced PC/PBT alloy materials and a preparation method thereof, wherein low-temperature impact property of the alloy is improved by adding a low-temperature toughening agent.
  • Polycarbonate / polybutylene terephthalate (PC/PBT) compositions are widely used in many applications such as automotive and other OVAD (Outdoor Vehicle and Devices) exteriors by its excellent property and processability, ductility (low temperature), resistance to chemical attack and weathering.
  • Compositions comprising polycarbonate and poly(ethylene terephthalate) (PC/PET) have been reported to have better thermal properties and more surface gloss compared to PC/PBT compositions. Additionally PET is a widely available, well-known material, used for a variety of applications including in particular bottles, such as for carbonated and non-carbonated soft drinks, fibers, and packaging, household and consumer products. PC/PET compositions are found to show less favorable low temperature ductility, i.e. ductility at temperatures in the range of about - 20 to about -30 °C. For achieving improved low temperature impact resistance properties, silicone-modified polycarbonate copolymer may be used, which, however is not cost effective.
  • It is, therefore, an object of the invention to provide for a composition comprising PC and PET that has improved low temperature impact resistance properties without significantly affecting or even improving the mechanical and other properties such as thermal properties.
  • To that extent the present inventors have surprisingly found that a composition comprising polycarbonate and polyester, wherein said polyester comprises poly(ethylene terephthalate), an impact modifier in combination with a specific ionomer demonstrates an improved low temperature impact resistance (without affecting mechanical and other thermal properties) compared to an otherwise identical composition wherein the poly(ethylene terephthalate) component does not contain the ionomer. Without willing to be bound to it, the present inventors believe that the presence of the specific monovalent ionomer acts as an impact synergist and helps by acting as intrinsically self-healable materials, which generates instantaneous impulsive fracture/ crack or propagation resistance without any external trigger. This makes it suitable for impact resistant application where better ductility is desired.
  • Accordingly the present invention relates to a thermoplastic composition comprising, based on the weight of the composition, at least 30 wt. % aromatic polycarbonate, at most 70 wt. % of polyester comprising poly(ethylene terephthalate), from 0.1 - 20 wt. % of an impact modifier, from 0.05 to 1.0 wt. % of a monovalent ionomer comprising repeat units derived from ethylene, a dicarboxylic acid or derivative thereof, a monocarboxylic acid, and optionally a comonomer.
  • For the avoidance of doubt it is noted that the composition according to the invention as presented herein is a thermoplastic composition.
  • By application of the invention the foregoing object is met, at least in part.
  • Polycarbonate
  • Polycarbonate is a well-known material and generally exhibits good mechanical and optical properties. Typical applications include optical media carriers, glazing, extruded sheets, lenses and water bottles. Polycarbonates are generally manufactured using two different technologies. In a first technology, known as the interfacial technology or interfacial process, phosgene is reacted with bisphenol A (BPA) in a liquid phase. Another well-known technology for the manufacture of polycarbonate is the so-called melt technology, sometimes also referred to as melt transesterification or melt polycondensation technology. In the melt technology, or melt process, a bisphenol, typically BPA, is reacted with a carbonate, typically diphenyl carbonate (DPC), in the melt phase. A polycarbonate obtained by the melt transesterification process is known to be structurally different from polycarbonate obtained by the interfacial process. In that respect it is noted that in particular the so called "melt polycarbonate" typically has a minimum amount of Fries branching, which is generally absent in "interfacial polycarbonate". Apart from that melt polycarbonate typically has a higher number of phenolic hydroxy end groups while polycarbonate obtained by the interfacial process is typically end-capped and has at most 150 ppm, preferably at most 50 ppm, more preferably at most 10 ppm of phenol hydroxyl end-groups.
  • In accordance with the invention, it is preferred that the polycarbonate comprises or consists of aromatic bisphenol A polycarbonate homopolymer (also referred to herein as bisphenol A polycarbonate) and not copolymers of polycarbonates. Preferably, the polycarbonate of the invention disclosed herein comprises at least 30 wt. %, preferably at least 60 wt. % of bisphenol A polycarbonate based on the total amount of polycarbonate. More preferably, the polycarbonate in the composition essentially consists or consists of bisphenol A polycarbonate.
  • It is preferred that the polycarbonate has a weight average molecular weight of 15,000 to 60,000 g/mol determined using gel permeation chromatography with polycarbonate standards.
  • In an aspect, the polycarbonate is an interfacial polycarbonate.
  • In another aspect, the polycarbonate is a melt polycarbonate.
  • In yet another aspect the polycarbonate is a mixture of from 20 - 80 wt. % of interfacial polycarbonate and from 80 - 20 wt. % of melt polycarbonate, based on the weight of the polycarbonate..
  • The polycarbonate may be a mixture of two or more polycarbonates differing in melt volume rate (i.e. in molecular weight). The polycarbonates of the mixture may both be a bisphenol A polycarbonate homopolymer.
  • Polyester
  • The polyester of the composition disclosed herein comprises, essentially consists of or consists of PET. The PET may be a mixture of two or more different poly(ethylene terephthalate)s, for example a mixture of PETs with mutually different intrinsic viscosities. The polyester may further comprise recycled poly(ethylene terephthalate).
  • Polyesters like poly(ethylene terephthalate) are known to a skilled person per se. In accordance with the invention the polyester can be prepared by direct polyesterification of terephthalic acid with 1,2-ethane diol (ethylene glycol), usually with the help of a strong acid catalyst in the presence or absence of co monomers like isophthalic acid (IPA).
  • It is preferred that the composition comprises at most 40 wt. % of polyester comprising poly(ethylene terephthalate) based on the weight of the composition and wherein the combined weight percent value of all components is 100 wt.%. It is preferred that the PET has an intrinsic viscosity of 0.4 to about 2.0 dl/g as measured in a 3:2 weight to weight mixture of phenol: 1,2-dichlorobenzene at 25°C.
  • In an aspect the polyester may further comprise another polyester, miscible with poly(ethylene terephthalate), which is preferably poly(butylene terephthalate) (PBT). In accordance with this aspect of the invention, the composition preferably comprises from 99 to 80 wt. % of poly(ethylene terephthalate) and 1 to 20 wt. % of poly(butylene terephthalate) based on the weight of the polyester.
  • Impact modifiers
  • The thermoplastic composition of the invention comprises an impact modifier. Suitable impact modifiers are typically high molecular weight elastomeric materials derived from olefins, monovinyl aromatic monomers, acrylic and methacrylic acids and their ester derivatives, as well as conjugated dienes. The polymers formed from conjugated dienes can be fully or partially hydrogenated. The elastomeric materials can be in the form of homopolymers or copolymers, including random, block, radial block, graft, and core-shell copolymers. Combinations of impact modifiers can be used.
  • The impact modifier is preferably selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene-methyl-acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, low density polyethylene, maleic anhydride grafted ethylene-octene copolymer, ethylene-ethyl acrylate-glycidyl ester copolymer, ethylene-butyl acrylate-glycidyl ester copolymer, rubber modified styrene-acrylonitrile copolymer, rubber modified styrene-acrylonitrile-methyl methacrylate copolymer, styrene-acrylonitrile copolymer and combinations of at least two of the foregoing (co)polymers.
  • The amount of impact modifier may be from 0.1 - 20 wt.% based on the weight of the composition. Preferably the impact modifier is comprised in the composition in an amount of from 2 - 15 wt.%, preferably from 8 - 12 wt.%.
  • Impact synergists
  • The composition of the invention comprises an impact synergist, which is a monovalent ionomer comprising repeat units derived from ethylene, a dicarboxylic acid or derivative thereof, a monocarboxylic acid, and optionally a comonomer.
  • Ionomers are synthetic polyelectrolytes that consist of both electrically neutral and ionized groups that are randomly and/or regularly distributed along the polymer backbone. One important characteristic of ionomers is the strong molecular aggregation of the ion-carrying groups to ion rich domains or ion clusters, which act as physical crosslinks. When heated, the ionic bonds and clusters dissolve and when cooled, they reform. This gives ionomers a unique structure and behavior. At low temperatures, they behave like crosslinked polymers (elastomers) and at elevated temperatures like ordinary thermoplastics. The majority of ionomers studied have a polyvinyl or polydiene backbone and carry anionic groups (anionomers) with Na+, and Zn2+ as counter ions.
  • These ionic copolymers have typically a low melting point, improved toughness/flexibility and mechanical strength and when used as films, possess a much higher clarity and gloss and provide superior hot tack, seal strength and puncture resistance than unmodified polyethylene film.
  • A well known ionomer is ethylene acrylic acid copolymer (EAA) which is sold under the tradename Surlyn by DuPont. It is frequently used as a food packaging material and as a tie-layer (compatibilizer) in multi-layer films. Other important applications include coatings and surface films for golf balls, sports equipment, and for over molded (cosmetic) bottles.
  • In accordance with the invention, the composition comprises from 0.05 to 1.0 wt. %, preferably from 0.1 to 0.5 wt. % of a monovalent ionomer comprising repeat units derived from ethylene, a dicarboxylic acid or derivative thereof, a monocarboxylic acid, and optionally a comonomer; based on the weight of the composition. The monocarboxylic acid is selected preferably from (meth)acrylic acid. The dicarboxylic acid is preferably selected from maleic acid, fumaric acid, itaconic acid, maleic anhydride, fumaric anhydride, itaconic anhydride, one or more C1-4 alkyl half ester of maleic acid, one or more Ci-4 alkyl half ester of fumaric acid, one or more C1-4 alkyl half ester of itaconic acid, or combinations of two or more thereof. The comonomers is preferably selected from CO, acid anhydride, maleic acid, monoester of the acid anhydride, an epoxy-containing (meth)acrylate, or combinations of two or more thereof.
  • The carboxylic acid functionalities in the aforesaid ionomer are at least partially neutralized (from about 10 to about 70 %, about 35 to about 70 %) by a monovalent ion, preferably selected from alkali metal ions, more preferably from sodium or potassium. Methods for preparing ionomers from copolymers are well known in the art.
  • Other additives
  • Typical additives that are used in the composition can comprise one or more of a flow modifier, filler, reinforcing agent (e.g., glass fibers or glass flakes), antioxidant, heat stabilizer, light stabilizer, UV light stabilizer and/or UV absorbing additive, plasticizer, lubricant, release agent, in particular glycerol monostearate, pentaerythritol tetra stearate, glycerol tristearate, stearyl stearate, antistatic agent, antifog agent, antimicrobial agent, colorant (e.g., a dye or pigment), flame retardant either or not combined with an anti-drip agent such as polytetrafluoroethylene (PTFE) or PTFE-5 encapsulated styrene-acrylonitrile copolymer.
  • The composition disclosed herein may comprise one or more nucleating agents. In that respect, the term nucleating agent refers to an additive that enhances the formation of crystals in the polyester phase of the composition. Addition of a nucleating agent will accordingly increase the crystallinity of the polyester phase, which results in an increased heat resistance. The composition may comprise from 0.01 to 5 wt.% by weight of nucleating agent(s).
  • The compositions can be manufactured by various methods known in the art. For example, polycarbonate, polyester, and other components are first blended, optionally with any fillers or additives, in a high-speed mixer or by hand mixing. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components can be incorporated into the composition by feeding it directly into the extruder at the throat and/or downstream through a side feeder, or by being compounded into a masterbatch with a desired polymer and fed into the extruder. The extruder was set with barrel temperatures between 150°C and 260°C. The extrudate can be immediately cooled in a water bath and pelletized. The pellets so prepared can be one-fourth inch long or less as desired. Such pellets can be used for subsequent molding, shaping, or forming.
  • Shaped, formed, or molded articles comprising the compositions are also provided. The compositions can be molded into articles by a variety of methods, such as injection molding, extrusion, and thermoforming. Some example of articles include automotive and vehicular body panels such as bumper covers and bumpers or a housing for electrical equipment.
  • Accordingly, the present invention relates to an article comprising or consisting of the composition disclosed herein. More in particular, the present invention relates to vehicular body parts or for housing of electrical equipment comprising or consisting the composition disclosed herein. Likewise, the present invention relates to a vehicle or an electrical equipment comprising said vehicular body part or said housing. The present invention relates to the use of the composition disclosed herein for the manufacture of an article of manufacture, such as an automotive part.
  • Composition
  • In accordance with the invention the composition comprises at least 30 wt. % aromatic polycarbonate and at most 70 wt. % of polyester comprising poly(ethylene terephthalate).
  • The amount of polycarbonate is preferably from 30 wt.% - 90 wt.% such as from 55 wt.% - 70 wt.% and the amount of polyester is preferably from 10 - 70 wt.% such as from 30 wt. % - 50 wt. %.
  • In an aspect, it is preferred that the monovalent ionomer is produced by neutralizing all or part of the carboxylic acid using a monovalent ion, preferably selected from alkali metal ions, more preferably from sodium or potassium.
  • For the avoidance of doubt the skilled person will understand that the total weight of the composition will represent 100 wt.% and that any combination of materials which would not form 100 wt.% in total is unrealistic and not according to the invention. Thus, the total of the components making up the thermoplastic composition disclosed herein is 100 wt.%.
  • The present invention will now be further elucidated based on the following non-limiting examples.
  • Test Methods
  • Impact Notched Izod impact (NII) properties were determined in accordance with to ISO 180/1A on injection molded samples being 80 x 10 x 4 mm in size. The test was carried out at different temperatures.23°C, -20°C and -30°C. The impact energy is expressed in kJ/m2. The test result is the average of 5 specimens.
    Intrinsic viscosity The intrinsic viscosity of the polyesters was measured in a 3:2 weight to weight mixture of phenol: 1,2-dichlorobenzene at 25°C.
    Vicat softening temperature (VST) The Vicat softening point (in °C) was determined in accordance with ISO 306 at a load of 50N and a speed of 120°C/hr on injection molded samples with dimension 10mm (length) X 10 mm (width) X 4 mm (thickness).
    Heat distortion temperature (HDT) The heat distortion temperature, HDT (in °C) was determined in accordance with ISO 75 flatwise at a load of 1.8 MPa.
    Molecular weight The molecular weight of the polycarbonate and poly(butylene terephthalate) was measured by GPC method with polystyrene standard in an Agilent 1260 Infinity (SYS-LC-1260) equipment with PLGel 5µm Minimix C 250 x4.6 mm column and Refractive Index detector. The sample is dissolved in dichloromethane and the same solvent is used as carrier.
    Fries branching The amount of Fries branching was determined using an Agilent 1100series HPLC equipped with a MWD G1365B detector. The column is an Agilent Zorbax Eclipse XDB-C18 4.6 x 75 mm. The injection volume is 50ml. The oven temperature is 35 °C and the wavelength to acquire data is 320.16 nm. For sample preparation 0.3g of sample is dissolved in 7.5 ml of a solvents mixture based on 5 ml of tetrahydrofuran and 2.5 ml of a 10 % of potassium hydroxide solution in methanol, after heating this sample at 40°C during 20 min, 1.4 ml of acetic acid is added.
    End Cap Level The endcap level was determined based on UV measurement to determine the amount of terminal OH groups. Combined with the number average molecular weight the endcap level is then determined in accordance with formula below.
    % EC = 100 ppmOH × Mn 340000
    Figure imgb0001
    wherein % EC is the endcap level, ppm OH is the amount of hydroxyl end groups in parts per million by weight and Mn is the number average molecular weight of the polycarbonate based on polycarbonate standards.
    The UV spectrophotometer was a Perkin Elmer Lambda 800. Measurements were carried out on 0.01g of a polycarbonate sample diluted in 10 ml of dichloromethane and placed into a quartz cuvette of 10 mm of optical path. The wavelength to acquire data are 284 and 292 nm. The results from the equipment as ppm of OH are used to calculate the endcap using also the molecular weight of the polycarbonate and according to the formula for calculation as disclosed herein.
    Tensile modulus The tensile modulus (in units of Giga pascals; GPa) and % nominal strain at break were tested according to ISO 527 measured at room temperature (23 °C).
    Tensile strength Tensile strength (in units of megapascals: MPa) and % elongation were tested according to to ISO 527 measured at room temperature (23 °C).
    Glass transition temperature (Tg) Glass transition temperatures were determined by dual cantiliver three point bending dynamic mechanical analyzer wherein the temperature was increased from 23 °C to 250 °C and frequency of 6.28 rad/sec.
    Melt volume rate (MVR) The melt volume rate was determined in accordance with ISO 1133-1:2011. For polycarbonate, measurements were carried out at a temperature of 300°C and a load of 1.2 kg. For the compositions, measurements were carried out at a temperature of 250°C and a load of 5.0 kg.
  • EXAMPLES
  • The examples were made by extruding on a WP 25 millimeter (mm) co-rotating intermeshing twin-screw extruder having L/D of 41. The components of the compositions and their source are listed in Table 1. All components were dry-mixed and added to the throat of the extruder. The extruder was set with barrel temperatures between 150°C and 260°C. The material was run maintaining torque of 55-60% with a vacuum of 100 millibar (mbar) - 800 mbar applied to the melt during compounding. The composition was pelletized after exiting the die head.
  • All samples were molded via injection molding with the molding machine set from 40 - 280°C and mold set at 100°C. Table 1: Components of the compositions and their source
    PC1 Bisphenol A polycarbonate manufactured using an interfacial process, having a melt volume rate of 6 cc/10 min, and endcap level of about 100%, available from SABIC (PC 105)
    PET1 Polyethylene terephthalate having an intrinsic viscosity of 0.84 dl/g as measured in a 3:2 weight to weight mixture of phenol: 1,2-dichlorobenzene at 25°C containing 1.85wt.% Isophthalic acid comonomer available from SABIC ( BC 212)
    IM1 MBS core shell impact modifier commercially available from Dow, Singapore (Paraloid MBS EXL 2690)
    Stab Stabilizer - hindered phenol Antioxidant Irganox 1010 from BASF
    Quench Mono Zinc Phosphate quencher
    Iono1 Surlyn PC100 , Na+ ionomer of ethylene acid copolymer, MFI 0.9 cc/10min, VST ∼ 60 °C, from DuPont
    lono2 Surlyn PC350 , Na+ ionomer of ethylene acid copolymer, MFI 4.5 cc/10min, VST ∼ 70°C, from DuPont
    lono3 Surlyn 1652, Zn2+ ionomer of ethylene acid copolymer, MFI 5.2 cc/10min, VST ∼ 80°C, from DuPont
    Nucl1 Jetfine Talc 3CA having mean particle size ∼ 1 micron-- from Imerys Clays
    Nucl2 Imerey Talc having mean particle size ∼ 2 micron-- from Imerys Clays
  • COMPARATIVE EXAMPLES (CE1) AND EXAMPLES (E1-4): Table 2
  • Table 2: Formulations and properties for the PC - PET composition with Na+ Ionomer impact synergist
    Components (wt. %) CE1 E1 E2 E3 E4
    PC1 59.87 59.50 59.50 59.70 59.40
    PET1 30.00 30.00 30.00 30.00 30.00
    Stab 0.05 0.10 0.10 0.10 0.10
    Quench 0.08 0.10 0.10 0.10 0.10
    Iono1 0.20
    lono2 0.20 0.10 0.40
    IM1 10.00 10.00 10.00 10.00 10.00
    Tensile Mod, GPa 2.1 2.1 2.0 2.1 2
    Tensile Strength, MPa 52 61 53 53 52
    Strain, break, % 129 140 123 120 121
    NII at 23C , kJ/m2 69 66 78 74 65
    NII at -20C, kJ/m2 49 111 104 55 71
    NII at -30C, kJ/m2 34 96 98 27 55
    HDT (1.8 Mpa), °C 92 92 92 94 91
    VST (120/50), °C 131 136 135 134 133
    Tg (PC) by DMA , °C 148.0 147.0 146.5 148.0 148.0
    Tg (PET) by DMA , °C 81.0 81.0 80.5 79.0 80.5
  • The amounts in Table 2 are in weight percent based on the total weight of the composition. In all the examples, the total amount of components, equals 100 weight percent. Table 2 shows that the composition comprising the Na+ ionomer impact synergist surprisingly shows improved low temperature (at -20°C and -30°C) impact resistance property, without compromising on the thermal properties as demonstrated by HDT, VST, Tg results. When comparing C1 with E1 & E2, it is observed there is an increase of at least two times in the low temperature impact resistance property resulting from the addition of the Na+ ionomer impact synergist. E3 & E4 shows similar experiments with lower and higher concentrations of the ionomers respectively.
  • COMPARATIVE EXAMPLES (CE1) AND EXAMPLES (E2 and E5): Table 3
  • E2 and E5 demonstrate the properties of the composition comprising the Na+ ionomer and the Zn++ ionomer impact synergists respectively. Comparing CE1 & E2 to E3, it can be seen that presence of Zn++ ionomer does not improve the low temperature impact properties as shown in Table 3. Table 3: Formulations and properties for the PC - PET composition with Na+ and Zn++ ionomer impact synergist
    Components (wt. %) CE1 E2 E5
    PC1 59.87 59.60 59.60
    PET1 30.00 30.00 30.00
    Stab 0.05 0.10 0.10
    Quench 0.08 0.10 0.10
    lono2 0.20
    lono3 0.20
    IM1 10.00 10.00 10.00
    Tensile Mod, GPa 2.1 2.0 2.1
    Tensile Strength, MPa 52 53 53
    Strain, break, % 129 123 127
    NII at 23C , kJ/m2 69 78 73
    NII at -20C, kJ/m2 49 104 20
    NII at -30C, kJ/m2 34 98 15
    HDT (1.8 Mpa), °C 92 92 86
    VST (120/50), °C 131 135 133
    Tg (PC) by DMA , °C 148.0 146.5 146.5
    Tg (PET) by DMA , °C 81.0 80.5 77.5
  • COMPARATIVE EXAMPLES (CE1) AND EXAMPLES (E2 and E6 - E9): Table 4
  • E6 and E7 demonstrate the use of different types of known nucleating agents to improve heat properties of PC/PET composition as shown by higher VST and HDT compared to CE1. However, these nucleating agents in E6 and E7 do not show any improvement in low temperature impact properties.
  • In E8 and E9, nucleating agents are added into the PC/PET composition comprising the Na+ ionomer impact synergist. No significant improvement in low temperature impact properties is observed, although improvement in heat properties are achieved. Table 4: Formulations and properties for the PC - PET composition with Na+ ionomer impact synergist in combination with nucleating agent
    Components (wt. %) CE1 E2 E6 E7 E8 E9
    PC1 59.87 59.60 59.60 59.60 59.60 59.40
    PET1 30.00 30.00 30.00 30.00 30.00 30.00
    Stab 0.05 0.10 0.10 0.10 0.10 0.10
    Quench 0.08 0.10 0.10 0.10 0.10 0.10
    Nucl1 0.20 0.20 0.10 0.20
    Nucl2 0.20
    lono2 0.10 0.20
    IM1 10.00 10.00 10.00 10.00 10.00 10.00
    Tensile Mod, GPa 2.1 2.0 2.2 2.2 2.1 2.1
    Tensile Strength, MPa 52 53 58 59 57 56
    Strain, break, % 129 123 126 130 135 131
    NII at 23C, kJ/m2 69 78 54 43 62 92
    NII at -20C, kJ/m2 49 104 14 12 8 31
    NII at -30C, kJ/m2 34 98 8 8 10 14
    HDT (1.8 Mpa), °C 92 92 96 97 97 96.5
    VST (120/50), °C 131 135 137 138 140 139
    Tg (PC) by DMA , °C 148.0 146.5 147.0 148.0 148.0 148.0
    Tg (PET) by DMA , °C 81.0 80.5 81.0 81.0 80.5 82.0

Claims (14)

  1. A thermoplastic composition comprising, based on the weight of the composition,
    at least 30 wt. % aromatic polycarbonate,
    at most 70 wt. % of polyester comprising poly(ethylene terephthalate),
    from 0.1 - 20 wt. % of an impact modifier,
    from 0.05 to 1.0 wt. % of a monovalent ionomer comprising repeat units derived from ethylene, a dicarboxylic acid or derivative thereof, a monocarboxylic acid, and optionally a comonomer.
  2. The composition of claim 1, wherein the monovalent ionomer is produced by neutralizing all or part of the monocarboxylic acid using a monovalent ion, preferably selected from alkali metal ions, more preferably sodium or potassium ions.
  3. The composition of claim 1 or 2 , wherein the monocarboxylic acid is (meth)acrylic acid; and the dicarboxylic acid or derivate thereof is preferably selected from maleic acid, fumaric acid, itaconic acid, maleic anhydride, fumaric anhydride, itaconic anhydride, one or more C1-4 alkyl half ester of maleic acid, one or more C1-4 alkyl half ester of fumaric acid, one or more C1-4 alkyl half ester of itaconic acid, or combinations of two or more thereof.
  4. The composition of any one or more of claims 1-3, wherein the amount of impact modifier is from 2 - 15 wt. %, preferably from 8 - 12 wt. %.
  5. The composition of any one or more of claims 1-4, wherein the polyester further comprises poly(butylene terephthalate).
  6. The composition of any one or more of claims 1-5 wherein the polyester comprises from 99 to 80 wt. % of poly(ethylene terephthalate) and 1 to 20 wt. % of poly(butylene terephthalate) based on the weight of the polyester.
  7. The composition of any one or more of claims 1-6 wherein the aromatic polycarbonate comprises or consists of bisphenol-A polycarbonate homopolymer.
  8. The composition of any one or more of claims 1-7 wherein the polycarbonate has a weight average molecular weight of 15,000 to 60,000 g/mol determined using gel permeation chromatography with polycarbonate standards and/or wherein the poly(ethylene terephthalate) has an intrinsic viscosity of 0.4 to about 2.0 dl/g as measured in a 60:40 phenol/tetrachloroethane mixture at 23°-30° C.
  9. The composition of any one or more of claims 1-8 wherein the impact modifier is selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene-methyl-acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, low density polyethylene, maleic anhydride grafted ethylene-octene copolymer, ethylene-ethyl acrylate-glycidyl ester copolymer, ethylene-butyl acrylate-glycidyl ester copolymer, rubber modified styrene-acrylonitrile copolymer, rubber modified styrene-acrylonitrile-methyl methacrylate copolymer, styrene-acrylonitrile copolymer and combinations of at least two of the foregoing (co)polymers.
  10. An article comprising or consisting of the composition of any one or more of claims 1-9.
  11. The article of claim 10, wherein the article is a vehicular body part or a housing for electrical equipment.
  12. A vehicle or an electrical equipment comprising the article of claim 11.
  13. Use of a composition of any one or more of claims 1-9 for the manufacture of an article, preferably an automotive part.
  14. Use of a monovalent ionomer comprising repeat units derived from ethylene, a dicarboxylic acid or derivative thereof, a monocarboxylic acid, and optionally a comonomer in a composition further comprising at least 30 wt. % aromatic polycarbonate, at most 70 wt. % of polyester comprising poly(ethylene terephthalate) and from 0.1 - 20 wt. % of an impact modifier for the manufacture of articles having improved low temperature impact properties as compared to an otherwise identical composition not containing the ionomer.
EP21156855.5A 2021-02-12 2021-02-12 Thermoplastic composition of polycarbonate and polyester Withdrawn EP4043526A1 (en)

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CN202280021350.9A CN117043271A (en) 2021-02-12 2022-01-18 Thermoplastic compositions of polycarbonates and polyesters
US18/276,964 US20240150571A1 (en) 2021-02-12 2022-01-18 Thermoplastic composition of polycarbonate and polyester
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Citations (5)

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Publication number Priority date Publication date Assignee Title
WO2002045098A2 (en) * 2000-11-30 2002-06-06 General Electric Company Conductive polyester/polycarbonate blends, methods for preparation thereof, and articles derived therefrom
JP2008115295A (en) 2006-11-06 2008-05-22 Mirai Kasei Kk Highly-processable polymer material
CN105255149A (en) 2015-11-05 2016-01-20 陕西省石油化工研究设计院 Low-temperature toughened and reinforced PC/PBT (polycarbonate/polybenzothiazole) alloy material and preparation method thereof
CN105385117A (en) 2015-10-27 2016-03-09 横店集团得邦工程塑料有限公司 High-/low-temperature-impact-resistance-enhanced flame-retardant PBT (Polybutylene Terephthalate) composite material for LED (Light Emitting Diode) aluminum-plastic structural parts and preparation method for PBT composite material
CN108034204A (en) 2017-12-28 2018-05-15 广东聚石化学股份有限公司 A kind of low-temperature impact-resistant polymer blend and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002045098A2 (en) * 2000-11-30 2002-06-06 General Electric Company Conductive polyester/polycarbonate blends, methods for preparation thereof, and articles derived therefrom
JP2008115295A (en) 2006-11-06 2008-05-22 Mirai Kasei Kk Highly-processable polymer material
CN105385117A (en) 2015-10-27 2016-03-09 横店集团得邦工程塑料有限公司 High-/low-temperature-impact-resistance-enhanced flame-retardant PBT (Polybutylene Terephthalate) composite material for LED (Light Emitting Diode) aluminum-plastic structural parts and preparation method for PBT composite material
CN105255149A (en) 2015-11-05 2016-01-20 陕西省石油化工研究设计院 Low-temperature toughened and reinforced PC/PBT (polycarbonate/polybenzothiazole) alloy material and preparation method thereof
CN108034204A (en) 2017-12-28 2018-05-15 广东聚石化学股份有限公司 A kind of low-temperature impact-resistant polymer blend and preparation method thereof

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